Hexagonal silicon-germanium nanowire branches with tunable composition.

Hexagonal SiGe-2H has been recently shown to have a direct bandgap, and holds the promise to be compatible with silicon technology. Hexagonal Si and Ge have been grown on an epitaxial lattice matched template consisting of wurtzite GaP and GaAs, respectively. Here, we present the growth of hexagonal Si and SiGe nanowire branches grown from a wurtzite stem by the vapor-liquid-solid growth mode, which is substantiated byin situtransmission electron microscopy. We show that the composition can be tuned through the whole range of stoichiometry from Si to Ge, and the possibility to realize Si and SiGe heterostructures in these branches.

Parity-preserving and magnetic field-resilient superconductivity in InSb nanowires with Sn shells.

Improving materials used to make qubits is crucial to further progress in quantum information processing. Of particular interest are semiconductor-superconductor heterostructures that are expected to form the basis of topological quantum computing. We grew semiconductor indium antimonide nanowires that were coated with shells of tin of uniform thickness. No interdiffusion was observed at the interface between Sn and InSb. Tunnel junctions were prepared by in situ shadowing. Despite the lack of lattice matching between Sn and InSb, a 15-nanometer-thick shell of tin was found to induce a hard superconducting gap, with superconductivity persisting in magnetic field up to 4 teslas. A small island of Sn-InSb exhibits the two-electron charging effect. These findings suggest a less restrictive approach to fabricating superconducting and topological quantum circuits.

Isotropic Atomic Layer Etching of ZnO Using Acetylacetone and O2 Plasma.

Atomic layer etching (ALE) provides Ångström-level control over material removal and holds potential for addressing the challenges in nanomanufacturing faced by conventional etching techniques. Recent research has led to the development of two main classes of ALE: ion-driven plasma processes yielding anisotropic (or directional) etch profiles and thermally driven processes for isotropic material removal. In this work, we extend the possibilities to obtain isotropic etching by introducing a plasma-based ALE process for ZnO which is radical-driven and utilizes acetylacetone (Hacac) and O2 plasma as reactants. In situ spectroscopic ellipsometry measurements indicate self-limiting half-reactions with etch rates ranging from 0.5 to 1.3 Å/cycle at temperatures between 100 and 250 °C. The ALE process was demonstrated on planar and three-dimensional substrates consisting of a regular array of semiconductor nanowires (NWs) conformally covered using atomic layer deposition of ZnO. Transmission electron microscopy studies conducted on the ZnO-covered NWs before and after ALE proved the isotropic nature and the damage-free characteristics of the process. In situ infrared spectroscopy measurements were used to elucidate the self-limiting nature of the ALE half-reactions and the reaction mechanism. During the Hacac etching reaction that is assumed to produce Zn(acac)2, carbonaceous species adsorbed on the ZnO surface are suggested as the cause of the self-limiting behavior. The subsequent O2 plasma step resets the surface for the next ALE cycle. High etch selectivities (∼80:1) over SiO2 and HfO2 were demonstrated. Preliminary results indicate that the etching process can be extended to other oxides such as Al2O3.

Efficient Green Emission from Wurtzite Al xIn1- xP Nanowires.

Direct band gap III-V semiconductors, emitting efficiently in the amber-green region of the visible spectrum, are still missing, causing loss in efficiency in light emitting diodes operating in this region, a phenomenon known as the "green gap". Novel geometries and crystal symmetries however show strong promise in overcoming this limit. Here we develop a novel material system, consisting of wurtzite Al xIn1- xP nanowires, which is predicted to have a direct band gap in the green region. The nanowires are grown with selective area metalorganic vapor phase epitaxy and show wurtzite crystal purity from transmission electron microscopy. We show strong light emission at room temperature between the near-infrared 875 nm (1.42 eV) and the "pure green" 555 nm (2.23 eV). We investigate the band structure of wurtzite Al xIn1- xP using time-resolved and temperature-dependent photoluminescence measurements and compare the experimental results with density functional theory simulations, obtaining excellent agreement. Our work paves the way for high-efficiency green light emitting diodes based on wurtzite III-phosphide nanowires.

Effective Surface Passivation of InP Nanowires by Atomic-Layer-Deposited Al2O3 with POx Interlayer.

III/V semiconductor nanostructures have significant potential in device applications, but effective surface passivation is critical due to their large surface-to-volume ratio. For InP such passivation has proven particularly difficult, with substantial depassivation generally observed following dielectric deposition on InP surfaces. We present a novel approach based on passivation with a phosphorus-rich interfacial oxide deposited using a low-temperature process, which is critical to avoid P-desorption. For this purpose we have chosen a POx layer deposited in a plasma-assisted atomic layer deposition (ALD) system at room temperature. Since POx is known to be hygroscopic and therefore unstable in atmosphere, we encapsulate this layer with a thin ALD Al2O3 capping layer to form a POx/Al2O3 stack. This passivation scheme is capable of improving the photoluminescence (PL) efficiency of our state-of-the-art wurtzite (WZ) InP nanowires by a factor of ∼20 at low excitation. If we apply the rate equation analysis advocated by some authors, we derive a PL internal quantum efficiency (IQE) of 75% for our passivated wires at high excitation. Our results indicate that it is more reliable to calculate the IQE as the ratio of the integrated PL intensity at room temperature to that at 10 K. By this means we derive an IQE of 27% for the passivated wires at high excitation (>10 kW cm-2), which constitutes an unprecedented level of performance for undoped InP nanowires. This conclusion is supported by time-resolved PL decay lifetimes, which are also shown to be significantly higher than previously reported for similar wires. The passivation scheme displays excellent long-term stability (>7 months) and is additionally shown to substantially improve the thermal stability of InP surfaces (>300 °C), significantly expanding the temperature window for device processing. Such effective surface passivation is a key enabling technology for InP nanowire devices such as nanolasers and solar cells.

Crystal Phase Quantum Well Emission with Digital Control.

One of the major challenges in the growth of quantum well and quantum dot heterostructures is the realization of atomically sharp interfaces. Nanowires provide a new opportunity to engineer the band structure as they facilitate the controlled switching of the crystal structure between the zinc-blende (ZB) and wurtzite (WZ) phases. Such a crystal phase switching results in the formation of crystal phase quantum wells (CPQWs) and quantum dots (CPQDs). For GaP CPQWs, the inherent electric fields due to the discontinuity of the spontaneous polarization at the WZ/ZB junctions lead to the confinement of both types of charge carriers at the opposite interfaces of the WZ/ZB/WZ structure. This confinement leads to a novel type of transition across a ZB flat plate barrier. Here, we show digital tuning of the visible emission of WZ/ZB/WZ CPQWs in a GaP nanowire by changing the thickness of the ZB barrier. The energy spacing between the sharp emission lines is uniform and is defined by the addition of single ZB monolayers. The controlled growth of identical quantum wells with atomically flat interfaces at predefined positions featuring digitally tunable discrete emission energies may provide a new route to further advance entangled photons in solid state quantum systems.

Plasma-assisted atomic layer deposition of conformal Pt films in high aspect ratio trenches.

To date, conventional thermal atomic layer deposition (ALD) has been the method of choice to deposit high-quality Pt thin films grown typically from (MeCp)PtMe3 vapor and O2 gas at 300 °C. Plasma-assisted ALD of Pt using O2 plasma can offer several advantages over thermal ALD, such as faster nucleation and deposition at lower temperatures. In this work, it is demonstrated that plasma-assisted ALD at 300 °C also allows for the deposition of highly conformal Pt films in trenches with high aspect ratio ranging from 3 to 34. Scanning electron microscopy inspection revealed that the conformality of the deposited Pt films was 100% in trenches with aspect ratio (AR) up to 34. These results were corroborated by high-precision layer thickness measurements by transmission electron microscopy for trenches with an aspect ratio of 22. The role of the surface recombination of O-radicals and the contribution of thermal ALD reactions is discussed.

Boosting Hole Mobility in Coherently Strained [110]-Oriented Ge-Si Core-Shell Nanowires.

The ability of core-shell nanowires to overcome existing limitations of heterostructures is one of the key ingredients for the design of next generation devices. This requires a detailed understanding of the mechanism for strain relaxation in these systems in order to eliminate strain-induced defect formation and thus to boost important electronic properties such as carrier mobility. Here we demonstrate how the hole mobility of [110]-oriented Ge-Si core-shell nanowires can be substantially enhanced thanks to the realization of large band offset and coherent strain in the system, reaching values as high as 4200 cm2/(Vs) at 4 K and 1600 cm2/(Vs) at room temperature for high hole densities of 1019 cm-3. We present a direct correlation of (i) mobility, (ii) crystal direction, (iii) diameter, and (iv) coherent strain, all of which are extracted in our work for individual nanowires. Our results imply [110]-oriented Ge-Si core-shell nanowires as a promising candidate for future electronic and quantum transport devices.

Growth and Optical Properties of Direct Band Gap Ge/Ge0.87Sn0.13 Core/Shell Nanowire Arrays.

Group IV semiconductor optoelectronic devices are now possible by using strain-free direct band gap GeSn alloys grown on a Ge/Si virtual substrate with Sn contents above 9%. Here, we demonstrate the growth of Ge/GeSn core/shell nanowire arrays with Sn incorporation up to 13% and without the formation of Sn clusters. The nanowire geometry promotes strain relaxation in the Ge0.87Sn0.13 shell and limits the formation of structural defects. This results in room-temperature photoluminescence centered at 0.465 eV and enhanced absorption above 98%. Therefore, direct band gap GeSn grown in a nanowire geometry holds promise as a low-cost and high-efficiency material for photodetectors operating in the short-wave infrared and thermal imaging devices.

Pseudodirect to Direct Compositional Crossover in Wurtzite GaP/InxGa1-xP Core-Shell Nanowires.

Thanks to their uniqueness, nanowires allow the realization of novel semiconductor crystal structures with yet unexplored properties, which can be key to overcome current technological limits. Here we develop the growth of wurtzite GaP/InxGa1-xP core-shell nanowires with tunable indium concentration and optical emission in the visible region from 590 nm (2.1 eV) to 760 nm (1.6 eV). We demonstrate a pseudodirect (Γ8c-Γ9v) to direct (Γ7c-Γ9v) transition crossover through experimental and theoretical approach. Time resolved and temperature dependent photoluminescence measurements were used, which led to the observation of a steep change in carrier lifetime and temperature dependence by respectively one and 3 orders of magnitude in the range 0.28 ± 0.04 ≤ x ≤ 0.41 ± 0.04. Our work reveals the electronic properties of wurtzite InxGa1-xP.

Functional nickel-based deposits synthesized by focused beam induced processing.

Functional nanostructures fabricated by focused electron/ion beam induced processing (FEBIP/FIBIP) open a promising route for applications in nanoelectronics. Such developments rely on the exploration of new advanced materials. We report here the successful fabrication of nickel-based deposits by FEBIP/FIBIP using bis(methyl cyclopentadienyl)nickel as a precursor. In particular, binary compounds such as nickel oxide (NiO) are synthesized by using an in situ two-step process at room temperature. By this method, as-grown Ni deposits transform into homogeneous NiO deposits using focused electron beam irradiation under O2 flux. This procedure is effective in producing highly pure NiO deposits with resistivity of 2000 Ωcm and a polycrystalline structure with face-centred cubic lattice and grains of 5 nm. We demonstrate that systems based on NiO deposits displaying resistance switching and an exchange-bias effect could be grown by FEBIP using optimized parameters. Our results provide a breakthrough towards using these techniques for the fabrication of functional nanodevices.

Strong reduction of spectral heterogeneity in gold bipyramids for single-particle and single-molecule plasmon sensing.

Single metal nanoparticles are attractive biomolecular sensors. Binding of analyte to a functional particle results in a plasmon shift that can be conveniently monitored in a far-field optical microscope. Heterogeneities in spectral properties of individual particles in an ensemble affect the reliability of a single-particle plasmon sensor, especially when plasmon shifts are monitored in real-time using a fixed irradiation wavelength. We compare the spectral heterogeneity of different plasmon sensor geometries (gold nanospheres, nanorods, and bipyramids) and correlate this to their size and aspect-ratio dispersion. We show that gold bipyramids exhibit a strongly reduced heterogeneity in aspect ratio and plasmon wavelength compared to commonly used gold nanorods. We show that this translates into a significantly improved homogeneity of the response to molecular binding without compromising single-molecule sensitivity.

Exploring Crystal Phase Switching in GaP Nanowires.

The growth of wurtzite/zincblende (WZ and ZB, respectively) superstructures opens new avenues for band structure engineering and holds the promise of digitally controlling the energy spectrum of quantum confined systems. Here, we study growth kinetics of pure and thus defect-free WZ/ZB homostructures in GaP nanowires with the aim to obtain monolayer control of the ZB and WZ segment lengths. We find that the Ga concentration and the supersaturation in the catalyst particle are the key parameters determining growth kinetics. These parameters can be tuned by the gallium partial pressure and the temperature. The formation of WZ and ZB can be understood with a model based on nucleation either at the triple phase line for the WZ phase or in the center of the solid-liquid interface for the ZB phase. Furthermore, the observed delay/offset time needed to induce WZ and ZB growth after growth of the other phase can be explained within this framework.

Cracking the Si Shell Growth in Hexagonal GaP-Si Core-Shell Nanowires.

Semiconductor nanowires have increased the palette of possible heterostructures thanks to their more effective strain relaxation. Among these, core-shell heterostructures are much more sensitive to strain than axial ones. It is now accepted that the formation of misfit dislocations depends both on the lattice mismatch and relative dimensions of the core and the shell. Here, we show for the first time the existence of a new kind of defect in core-shell nanowires: cracks. These defects do not originate from a lattice mismatch (we demonstrate their appearance in an essentially zero-mismatch system) but from the thermal history during the growth of the nanowires. Crack defects lead to the development of secondary defects, such as type-I1 stacking faults and Frank-type dislocations. These results provide crucial information with important implications for the optimized synthesis of nanowire-based core-shell heterostructures.

Encapsulation method for atom probe tomography analysis of nanoparticles.

Open-space nanomaterials are a widespread class of technologically important materials that are generally incompatible with analysis by atom probe tomography (APT) due to issues with specimen preparation, field evaporation and data reconstruction. The feasibility of encapsulating such non-compact matter in a matrix to enable APT measurements is investigated using nanoparticles as an example. Simulations of field evaporation of a void, and the resulting artifacts in ion trajectory, underpin the requirement that no voids remain after encapsulation. The approach is demonstrated by encapsulating Pt nanoparticles in an ZnO:Al matrix created by atomic layer deposition, a growth technique which offers very high surface coverage and conformality. APT measurements of the Pt nanoparticles are correlated with transmission electron microscopy images and numerical simulations in order to evaluate the accuracy of the APT reconstruction.

Sub-nanometer dimensions control of core/shell nanoparticles prepared by atomic layer deposition.

Bimetallic core/shell nanoparticles (NPs) are the subject of intense research due to their unique electronic, optical and catalytic properties. Accurate and independent control over the dimensions of both core and shell would allow for unprecedented catalytic performance. Here, we demonstrate that both core and shell dimensions of Pd/Pt core/shell nanoparticles (NPs) supported on Al2O3 substrates can be controlled at the sub-nanometer level by using a novel strategy based on atomic layer deposition (ALD). From the results it is derived that the main conditions for accurate dimension control of these core/shell NPs are: (i) a difference in surface energy between the deposited core metal and the substrate to obtain island growth; (ii) a process yielding linear growth of the NP cores with ALD cycles to obtain monodispersed NPs with a narrow size distribution; (iii) a selective ALD process for the shell metal yielding a linearly increasing thickness to obtain controllable shell growth exclusively on the cores. For Pd/Pt core/shell NPs it is found that a minimum core diameter of 1 nm exists above which the NP cores are able to catalytically dissociate the precursor molecules for shell growth. In addition, initial studies on the stability of these core/shell NPs have been carried out, and it has been demonstrated that core/shell NPs can be deposited by ALD on high aspect ratio substrates such as nanowire arrays. These achievements show therefore that ALD has significant potential for the preparation of tuneable heterogeneous catalyst systems.

Direct band gap wurtzite gallium phosphide nanowires.

The main challenge for light-emitting diodes is to increase the efficiency in the green part of the spectrum. Gallium phosphide (GaP) with the normal cubic crystal structure has an indirect band gap, which severely limits the green emission efficiency. Band structure calculations have predicted a direct band gap for wurtzite GaP. Here, we report the fabrication of GaP nanowires with pure hexagonal crystal structure and demonstrate the direct nature of the band gap. We observe strong photoluminescence at a wavelength of 594 nm with short lifetime, typical for a direct band gap. Furthermore, by incorporation of aluminum or arsenic in the GaP nanowires, the emitted wavelength is tuned across an important range of the visible light spectrum (555-690 nm). This approach of crystal structure engineering enables new pathways to tailor materials properties enhancing the functionality.

Texture of cellulose microfibrils of root hair cell walls of Arabidopsis thaliana, Medicago truncatula, and Vicia sativa.

Cellulose is the most abundant biopolymer on earth, and has qualities that make it suitable for biofuel. There are new tools for the visualisation of the cellulose synthase complexes in living cells, but those do not show their product, the cellulose microfibrils (CMFs). In this study we report the characteristics of cell wall textures, i.e. the architectures of the CMFs in the wall, of root hairs of Arabidopsis thaliana, Medicago truncatula and Vicia sativa and compare the different techniques we used to study them. Root hairs of these species have a random primary cell wall deposited at the root hair tip, which covers the outside of the growing and fully grown hair. The secondary wall starts between 10 (Arabidopsis) and 40 (Vicia) µm from the hair tip and the CMFs make a small angle, Z as well as S direction, with the long axis of the root hair. CMFs are 3-4 nm wide in thin sections, indicating that single cellulose synthase complexes make them. Thin sections after extraction of cell wall matrix, leaving only the CMFs, reveal the type of wall texture and the orientation and width of CMFs, but CMF density within a lamella cannot be quantified, and CMF length is always underestimated by this technique. Field emission scanning electron microscopy and surface preparations for transmission electron microscopy reveal the type of wall texture and the orientation of individual CMFs. Only when the orientation of CMFs in subsequent deposited lamellae is different, their density per lamella can be determined. It is impossible to measure CMF length with any of the EM techniques.

Remote p-doping of InAs nanowires.

We report on remote p-type doping of InAs nanowires by a p-doped InP shell grown epitaxially on the core nanowire. This approach addresses the challenge of obtaining quantitative control of doping levels in nanowires grown by the vapor-liquid-solid (VLS) mechanism. Remote doping of III-V nanowires is demonstrated here with the InAs/InP system. It is especially challenging to make p-type InAs wires because of Fermi level pinning around 0.1 eV above the conduction band. We demonstrate that shielding with a p-doped InP shell compensates for the built-in potential and donates free holes to the InAs core. Moreover, the off-current in field-effect devices can be reduced up to 6 orders of magnitude. The effect of shielding critically depends on the thickness of the InP capping layer and the dopant concentration in the shell.

Hydrogen 21-centimeter emission from a galaxy at cosmological distance.

We have detected the neutral atomic hydrogen (HI) emission line at a cosmologically significant distance [redshift (z) = 0.18] in the rich galaxy cluster Abell 2218 with the Westerbork Synthesis Radio Telescope. The HI emission originates in a spiral galaxy 2.0 h65(-1) megaparsecs from the cluster core. No other significant detections have been made in the cluster, suggesting that the mechanisms that remove neutral gas from cluster galaxies are efficient. We infer that fewer than three gas-rich galaxies were accreted by Abell 2218 over the past 10(9) years. This low accretion rate is qualitatively consistent with low-density cosmological models in which clusters are largely assembled at z > 1.